Halohydrin reacted aromatic amine polymer



Patented Feb l8, 1947 o 2,416,262

S PATENT OFFICE HALOHYDRIN REACTED AROMATIC AMINE POLYMER Samuel S. Kistler, West Boylston, Mass., assignor to Norton Company, Worcester, Mass., a corporation of Massachusetts No Drawing. Original application September 17,

1941, Serial No. 411,249. Divided and this 'application April 18, 1944, Serial No. 531,651

UNITED STATE 7 Claims. 1

This invention relates to resinous compositions and methods of making the same.

This application is a division of my copending application Serial No. 411,249, filed September 17, 1941, which was a continuation in part of a copending application Serial No. 318,004, filed February 8, 1940, which in turn was a division of my prior application Serial No. 306,545, filed November 28, 1939, and patented February 10, 1942, No. 2,272,873.

One object of the invention is to provide a new type of resin.

pointed out hereinafter.

According to this invention, I have provided resinous compositions, and particularly polymeric resinous compositions comprising the reaction product of a halogenated organic compound, an aliphatic halohydrin, or of such a halogenated organic compound and an aldehyde, such as formaldehyde or furfural, with the condensation product of an aldehyde and a primary aromatic amine. The halogenated organic compound alkylates the amino nitrogens of the aldehyde-amine condensation product, typically forming an alkylene or substituted alkylene cross-link between nitrogen atoms of adjacent moleculesof the condensation. product. Halohydric acid from the halogen ated compound adds on to at least a portion of the nitrogen atoms to form halohydric salt combinations therewith. When an aldehyde is also reacted with the aldehyde-amine condensation product, further cross-:linkages are formed, typically iinking aromatic rings of adjacent molecules of the condensation product with methylene 'or substituted methylene radicalsattached to the a quantity of an aldehyde, such as formaldehyde or furfural; and an organic compound containing a halogen selected from the group consisting of chlorine and bromine and capable of "splitting off hydrogen halide at elevated temperatures and/or of alkylating an aromatic amine polymer, providing cross links connecting amine groups of the chains. The aromatic amine which I now prefer to use is aniline. According to the invention,

aniline or other primary aromatic amine is reacted with formaldehyde, I-ICHO, or with furfural mama in the presence of a strong acid to produce --a long chain polymer which, when an excess of formaldehyde or furfural above the stoichiometric proportions is used, for example 20% excess, has adjacent chains connected with methylene, CH2,' or substituted methylene groups to form a tough, heat resistant, senilthermoplastic resin. I may add some of the aldehyde after the initial condensation, and my invention clearly contemplates that one aldehyde may be used at one stage, and a different aldehyde may be used at another stage.

As .examples of the halogenated organic compound, I may use any aliphatic halohydrin of not more than five carbon atoms, such as any of the amylene chlorohydrins, propylene chlor'ohydrin, any of the butylene chlorohydrins, ethylene chlorohydrin, ethylene bromohydrin, glycerol alpha gamma dichlorohydrin. Most of the examples are chlorinated compounds because these are cheaper and more readily available than the and especially for use as the binder for sandhydrochloric acid.

paper orabrasive cloth, and for abrasive discs, 1 and for the" adhesive for abrasive coated polishing wheels such as are referred to as set-up wheels. However, the principal use of the resin I of my invention is for the bond of grinding wheels, and other solid abrasive articles, such as segments, sectors, honing sticks and the like. ,Accordingly, whereas it should be understood that 1 the resin may be formed without abrasive filler, or with any other filler, such as sawdust, graphite, j carbon,'asbestos, cloth or quartz, in the examples 3 I shall describe the manufacture of grinding wheels. The technique for manufacturing other j solid abrasive articles is substantially the same.

I, therefore, provide a quantity of abrasive grain. Any abrasive grain may be used, for example, any of the varieties of alumina, such as emery, corundum, dense regular fused alumina, f porous fused alumina, silicon carbide, and other j hard carbides, quartz, glass. garnet or diamonds. Considering now specific examples of the manufeature of grinding wheels in accordance with i the present invention, I may proceed'as follows:

} Example I Eight hundred and fifty-eight cubic centi- After standing for Twenty-eight and one tenth pounds of a porous,

relatively pure grade fused alumina abrasive, No. i 20 grit size, is now wet with twenty-three hundredths of 'a pound of furfural. jtenths pounds of the above mixture of aniline formaldehyde resin and the ethylene chlorohye 'drin are intimately mixed with the fused alumina ;wet with furfural, spread in an eighteen inch 1 mold with a five inch arbor, and hot pressed for one hour and a half at a temperature of 160 C. iunder a pressure of three tons per square inch.

The wheel is then stripped from the'mold.

Five and nine- As conducive to a clearer understanding of the present invention I believe that a typical f structural formula of the resin thus produced is I j as follows:

The above is the modified polymer formed-when ethylene chlorohydrin is used. It will be noted that the nitrogen atoms of the secondary amine groups are connected by the ethylene chlorohydrin. Hydrogen chloride is found attached to some of the secondary amine groups. Other secondary amine groups have lost'the elements of water. Furyl methylene groups are shown connecting some of the points on the benzene rings ortho to the secondary amine groups. These furyl methylene groups were derived from the furfural used to plasticize the abrasive grain. Naturally if enough furfural is used all of these ortho points will be connected, while if less than the saturatin amount is used, only some of the ortho points will be connected. These furyl methylene groups forming connecting links add strength to i the resin. If furfural, however, was used to condense the aniline formaldehyde, furyl rings would substltutefor one of the hydrogen atoms'on the connecting methylene groups.

As a subexample within the general framework of Example I, if glycerol alpha gamma dichlorohydrin be substituted for the ethylene chlorohy- 5 meters of aniline is dissolved in eight liters of water containing nine and three-tenths mole of To this is added eight hundred and fifty cubic centimeters of formalin solution containing four tenths gram of formaldel hyde per cubic centimeter. 3 one hour a quantity of sodium hydroxide is added 3 equivalent to the hydrochloricacid present. The precipitated resin is filtered, washed, dried, and {ground to a fine powder. Into each tenpounds of this powdered resin I mix two-and'two-tenths pounds of ethylene chlorohydrin.

drin, approximately the following structure may Thus it will be seen that if ethylene bromohydrin is used (in sufllcient quantity) one-half of the'secondary amine groups will have. hydrogen bromide attached to them and the other half of the secondary amine groups will have elements of water attached to them. If any of the alpha butylene chlorohydrin, beta butylene chlorohydrin, propylene'chlorohydrin or any of the amylene chlorohydrinsare used, in sufiicient quantity, one half of the secondary amine groups will have hydrogen chloride attached to them and the other half of the secondary amine groups will have the elements of water attached to them. Also in the case of these last named compounds the connecting halohydrin groups will be branched because the amino groups. attach to the carbon atoms having halogen attached and also having hydroxyl attached.

These compounds have'the property of giving off hydrogen chloride (or' hydrogen bromide) when heated to a temperature of 500 C. When the temperature drops far below that point they no longer give up the hydrogen halide.

Example II Thirty-seven pounds of filo. 14 mesh fused alumina abrasive is placed in a mixing pan and wet with five hundred and forty cubic centimeters of furfural. To this are added nine pounds of the resin and halohydrin mixture of Example I and two pounds of cryolite; Further mixing is caused and then the mixture thus produced (which is substantially what is called a dry granular mix) is spread in a sixteen inch mold with a six inch arbor and hot pressed for two hours at a temperature of 160 C. and under a pressure I of five hundred tons. Such a wheel will give as good a finish on stainless steel as a rubber wheel but is much more durable.

It may be noted at this point that cold pressing can be resorted to by reason of the plasticizing of the abrasive grains with furfural. However, the results are not as satisfactory as when the hot pressing method is used. Furthermore, the addition of furfural definitely increases the plasticity of the mix and provides a, better product when hot pressed.

Example III Eight hundred and fifty-eightcubic centimeters of aniline were dissolved in eight liters of water containing nine and three-tenths 'mols of hydrochloric acid. To this was added seven hundred and fifty cubic centimeters of formalin solution containing four-tenths grams of formaldehyde per cubic centimeter. After standing for one hour, a quantity of sodium hydroxide was added equivalent to the hydrochloric acid pres-'1. ent. The precipitated resin was filtered, washed,

Example IV Eight hundred and eighty-five grams of 60 mesh fused alumina is wet with twenty-two cubic centimeters of furfural. To the thus wet abrasiv grain are added one hundred and sixty grams of the powdered resin from Example III and fifty grams of ethylene bromohydrin. This mixture is spread in an eight inch mold and pressed at a temperature of 175 C. under a pressure of one hundred and fifty tons for half an hour. This wheel has characteristics similar to the wheels of the other examples.

, Example V Ten hundred and seventy grams of meta toluidine, CH3CcH-1NH2, is dissolved in eight liters of water containing ten mols of hydrochloric acid. To this solution is added eight hundred and fifty cubic centimeters of forty per cent formalin. After standing one hour, a quantity of sodium hydroxide is added equivalent to the .hydrochloric acid used. The precipitated resin is filtered, washed, dried, and ground to a fine powder.

Eight hundred and eighty-five grams of 60 mesh fused alumina is first wet with thirty cubic centimeters of furfural. Then one hundred and sixty grams of the powdered resin from Example V and twenty grams of propylene chiorohydrin are added and mixed to produce a dry granular mix. This mixture is spread in an eight inch mold and pressed under a pressure of two hundred tons then stripped from the mold and the green wheel is baked in an autoclave at a pressure of seven atmospheres at a temperature gradually rising to 175 C. and maintained at this temperature for three hours. The structure of the resin may be represented as follows:

on, H\ 01 on;

10 I on t I -vn n-c l L i l. f -i- OH: ,:H' 0'': CH:

Interpreting the foregoing diagrams, it 'must, be understood that an approximate condition is what is illustrated. It would be impossible to illustrate all of the linkages. Furthermorejfor an absolutely accurate representation, a-three dimensional structure would have to be represented.

For the acid used in condensing the resin, besides hydrochloric and phosphoric acids, any of the following acids or many others may also be used: Hydriodic acid Tri-chloro aceticacid Di-chloro acetic acid Maleic acid oxalic acid Sulphuric acid The requirement is that the acid should be at least as strong as phosphoric acid to give the best results.

Considering now the various features of this invention, when aniline is condensed with formaldehyde in the presence of a strong acid, we may have the following resin structure:

When furfural is used to condense the aniline, we may have the following resin structure:

In each of the above cases the use of enough aldehyde to cross link has been assumed. Similar structural formulae may be written for meta toluidine, meta phenylene diamine and diamino diphenyl methane. When furfural is substituted 0 in whole or in .part for formaldehyde for the original condensation process, a furyl group wil be found replacing one hydrogen atom attache to the carbon of some of the methylene grou connecting the amino groups to the opposite ring I It will be seen that it is more advantageous t 1 in the claims.

pla'sticize the abrasive grains with furfural because thereby a number of additional linkages are 1 provided in the polymeric structure, making it stronger.

It maybe noted at this point that cold pressing can be resorted to by reason of the plasticizing of the abrasive grains with furfural'. However,

3 the results are not as satisfactory as when the 1 hot pressing method is used. Furthermore, the addition of furfural definitely increases the Plasi ticity and provides a better product when hot pressing.

The reaction of the halogenated organic com- 1 pound with th condensation product appears to cross link and alkylate the condensation prodnot .at the amino groups and it is believed that typical resinous products. ofpthe invention may i be represented --by the following general structural formula, which is repeated in a complex 1 chain g wherein X is selected from the group consisting 1 of H and I Y is selected from the group consisting of H, NH; and CHs, Hal is selected from the group consisting of'Cl and Br, R is a bivalent radical 3 droxylated alkylene radicals, the adjacent Zs selected from the group consisting of alkylene 5 radicals, halogenated alkylene radicals, and hyproin'mately one molecular proportion of acid.

at least as strong as phosphoric acid and reacted by heating at resin curing temperatures with from about 9.31% to about 23.44% on the weight of the reactants of an aliphatic halohydrin containing from 2 to five carbon atoms and wherein the halogen is selected from of chlorine and bromine.

2. A halogenated cross linked aromatic amine polymer consisting of a condensation product of one molecular proportion of aniline and at least one molecular proportion of aldehyde selected from the group consisting of formaldehyde and furfural, condensed in the presence of at least approximately one molecular proportion of acid at least as strong as phosphoric acid and reacted by heating at resin curing temperatures with from about 9.31% to about 23.44% on the weight of the reactants of an aliphatic halohydrin containing from 2 to five carbon atoms and wherein the halogen is selected from the group consisting of chlorine and bromine.

3. A halogenated cross linkedaromatic amine one molecular proportion of primary aromatic amine selected from the group consisting of maybe hydrogen or a methylene or furyl bridge d between adjacent'benzene rings, and W reprel sents a radical selected from the group consisting of Cl, Br and OH.

While I have mentioned specific curing temi peratures, it should be understood that the up- I per limitisdetermined only by the decomposi- 1 tion point of'theresin. Temperatures short of 190 C. are safe. 1 temperature can be used but preferably above 60 C. but the lower the temperature, the more time to jcarry the'reaction to completion. Practical results can be obtained with temperatures above 90- C.

At the lower end, almost any The percentage of the propylene chlorohydrin to thereactants including the propylene chlorohydrin in Example V is 9.31%. The percentage of the amylene chlorohydrin to the reactants including the amylene-chlorohydrin in Example 111 j is 23.44%. The percentage in Example V is the lowest percentage of all of the examples and the percentage in Example III is the highest per- ;centage of all of theexamples, so therefore the range of about 9.31% to about 23.44% is used 'It will thus be seen that'there has been proabove invention and as the art herein described ;vided by this invention a composition of matter, I a'n article of manufacture, and an. art in which j the various objects hereinabove set forth together with many thoroughly practical advantages are successfully achieved.- As various possible em- ;bodiments might be made of the features of the aniline, meta phenylene diamine, meta toluidine and diamino diphenyl methane and at least one molecular proportion of formaldehyde, condensed in the presence of at least approximately one molecular proportion of acid at least as strong as phosphoric acid and reacted by heatingat resin curing temperatures with from about 9.31% to about 23.44% on the weight of thereactants of an aliphatic halohydrin containing from 2 to five carbon atoms and wherein the halogen is selected from the group consisting of chlorine and bromine.

4. A halogenated cross linked aromatic amine polymer consisting of a condensation product of one molecular proportion of aniline and at least one molecular proportion of aldehyde'consisting at least in part of formaldehyde, condensed in the presence of at least approximately one molecular proportion of acid at least as strong as phosphoric acid and reacted by heating at resin curing temperatures with from about 9.31%

to about 23.44% on the weight of the reactants of an aliphatic halohydrin containing from 2 to five carbon atoms and wherein the halogen is selected from the group consisting of chlorine and bromine.

5. A halogenated cross linked aromatic amine polymer according to claim 1 in which the alithe group consisting 9 in which the halogen is selected from the group consisting of chlorine and bromine.

7. A halogenated cross linked aromatic amine polymer according to claim 1 in which the aliphatic halohydrin is a propylene halohydrin and in which the halogen is selected from the group consisting of chlorine and bromine.

SAMUEL S. KISTIER.

REFERENCES CITED The following references are of record in the file of this patent:

Number 1,969,744 5 2,038,142 2,197,857 2,331,446

10 Number UNITED STATES PATENTS Name Date Gams Aug. 14, 1934 Sutter Apr. 21, 1936 Widmer (1) "Apr; 16, 1940 Widmer (2) pct. 12, 1943 FOREIGN PATENTS s Country Date :5. French Aug. 9. 1937 German Nov. 19, 1932 

